2-amino-4-alkylsulfonyl-5-nitrothiazole azo compounds



2-AMINO-4-ALKYLSULFONYL-S-NITROTHIAZOLE AZO COMPOUNDS Edmund B. Towne, Joseph B. Dickey, and Melvin S.

Bloom, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey t No Drawing. Application April 1, 1955 Serial No. 498,752

1 Claim. (Cl. 260-155) wherein R represents an alkyl group having 1 to 4 carbon atoms and Q represents a tetrahydroquinoline cou pling component joined to the azo bond through; the carbon atom in its 6-position, a benzomorpholine coupling component joined to the azo bond through the carbon atom in its 6-position, the radical of a 5-pyraz0lone com pound joined to the azo bond through the carbon atom in its 4-p'os'ition, the radical of barbituric acid, the radical of 2-iminobarbituric acid, the radical of thiobarbituric acid or the radical of 4-iminothiobarbituric acid. The

are useful for coloring cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof, nylon, wool, acrylonitrile graft polymers, and polyesters, such as polyethylene terephthalate. Ordinarily they are applied to textile materials made of said materials although in the case of the synthetic materials coloration can also be efiected, for example, by incorporating the azo. compounds into the spinning dope and spinning the fiber as usual. Generally speaking the dyeings obtained have excellent dischargeability and resistance to sublimation and good fastness to gas.

By cellulose alkyl carboxy-lic acid esters having two to four carbon atoms in the acid groups thereof, we mean to include, for example, both hydrolyzed and unhydrolyzed cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate and cellulose acetate-butyrate.

The new monoazocompounds of our invention are prepared by diazotising a 2-amin0-4-alkylsulfony1-5-nitrothiazole compound having the formula:

wherein R represents an alkyl group having 1 to 4 carbon atoms and coupling the diazonium compound obtained with barbituric acid, Z-iminobarbituric acid, thiobarbituric acid, 4-iminothiobarbituric acid, a tetrahydroquinoline coupling component, a benzomorpholine coupling component or a S-pyrazolone coupling component.

2-amino-4-methylsulfonyl-S-nitrothiazole, 2 amino-4- ethylsulfonyl-S-nitrothiazole, 2-amino-4-n-propylsulfony1- 1511 dmxynropyl 7 bromobenzomorpholine, 1 g dih S-nitrothiazole, 2-amino-4-isopropylsulfonyl-S-riitrothiazole and 2-amino-4-n-butylsulfonyl-5-nitrothiazole are representative of the S-nitrothiazole compounds used in the preparation of the azo compounds of our invention.

When a, tetrahydroquinoline or a benzomorpholine.

' tetrahydroquinoline,

compound is to be used as the coupling component the use of such compounds having the formulas:

2 0/ H2 and (3H2 0/ respectively, wherein R represents a hydroxyalkyl group having 2 to 4, inclusive, carbon atoms, Q represents a hydrogen atom or a methyl group and X represents a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group appearsto be advantageous and is preferred.

Illustrative of the alkyl groups represented by R are themethyl, the ethyl, the n-propyl, the isopropyl and the n-butyl groups. Similarly, the ,B-hydroxyethyl, the B-hydroxypropyl, the -hydroxypropyl, the 8,'y-dihydroxypropyl, the ,B-methyLpL'y-dihydroxypropyl and the 6-hydroxybutyl groups are illustrative of the hydroxyalkyl groups R represents.

Tetrahydroquinoline, 1-ethyltetrahydroquinoline, l-fihydroxyethyltetrahydroquinoline, 1-p','y-dihydroxypropyI tetrahydroquinoline, l-;3methyl-p3, ;-dihydroxypropyltetrahydroquinoline, l-'y hydroxypropyltetrahydroquinoline, l-d-hydroxybuty-ltetrahydroquinoline, l-B hydroxyethyl- 2,7-dimethyltetrahydroquinoline, 1-/8,' -dihydroxypropyl- 2,7-dimethyltetrahydroquinoline, l-fiyy-dihy droxypropyl- 2 methyltetrahydroquinoline, 1fi,v-dihydroxypropyl-7- methyltetrahydroquinoline, 1 2, dihydroxypropyl 7- chlorotetrahydroquinoline, 1 ,S y dihydroxypropyl-7- bromotetrahydroquinoline, l18, -dihydroxypropyl-7-fluorotetrahydroquinoline, 1-/3-hydroxyethy1-7-ethyltetrahydroquinoline, 1-fi-hydroxyethyl-7-methoxytetrahydroquinoline, 1' 8 methyl-p,' -dihydroxypropyl-7-ethoxytetrahydroquinoline, 1-/8 methoxyethy1tetrahydroquinoline, l-fiethoxyethyltetrahydroquinoline, I-fi-cyanoethyltetrahydroquinoline, 1-B-carbomethoxyethyltetrahydroquinoline, l-B- carboethoxyethyltetrahydroquinoline,, 1 2,2,2 trifluoroethyltetrahydroquinoline, 1-4,4,4-trifluorobutyltetrahydroquinoline, 1 2,2-difluoroethyltetrahydroquinoline, l-3,3- difiuoropropyltetrahydroquinoline, l-2,2 difluoropropyll-4,4-dilluoroamyltetrahydroquinoline, 1-,9-hydroxypropyl-2,7-dimethyltetrahydroquinoline, and" l-a-llyltetrahydroquinoline are illustrative of the tetrahydroquinoline coupling components used in the preparation of the azo compounds of our invention.

Similarly, benzomorpholine, l-ethylbenzomorpholine, 1- -13 hydroxyethylbenzomorpholine, 1 [5w dihydroxypropylbenzomorpholine, l 18 methyl ,B,'y dihydroxypropylbenzomorpholine, 1 'y hydroxypropylbenzomorpholine, l B hydroxybutylbenzomorpholine, l B hydroxyethyl 2,7 dimethylbenzomorpholine, l [3,7 dihydroxypropyl 2,7 dimethylbenzomorpholine, 1 5,

dihydroxypropyl 2 methylbenzomorpholine; 1 [3,7- dihydroxypropyl 7 methylbenzornorpholine, l flgy-dihydroxypropyl 7 chlorobenzomorpholine, 1 fi,'y-dihydroxypropyl 7 fiuorobenzomorpholine, 1 ,8 hydroxyethyl 7 ethylbenzomorpholine,l [3 hydroxyethyl- 7 methoxybenzomorpholine, 1 t3 methyl BJY dihydroxypropyl 7 ethoxybenzomorpholine, 1 e meth- L oxyethylbenzomorpholine, 1 ,8 4 ethoxyethylbenzomor Patented June 17, 1958 ethers, dialkyl maleates, alkenyl ketones, dialkyl furna- 4 monoethylenic monomer, including any of the monomers enumerated hereinabove, with the preformed live or dead pholine,1 ,8 cyanoethylbenzomorpholine, 1 B carbomethoxyethylbenzomorpholine, 1 [3 carboethoxyethylbenzomorpholine, 1-2,2,2 trifluoroethylbenzomorphohomopolymer or interpolymer whereby the acrylonitrile line, 1-4,4,4 trifluorobutylbenzomorpholine,- 1-2,2 dialone or together with another grafting monomer is comfluoroethylbenzomorpholine, 1-3,3 difluoropropylbenzo- 5 bined with the preformed polymer molecule to give a morpholine, l2,2 difiuoropropylbenzomorpholine, 1-4, graft polymer containing from 5 to 95% by weight of 4 difluoroamylbenzomorpholine, 1 fl hydroxypropylcombined acrylonitrile. 2,7 dimethylbenzomorpholine and l-allylbenzomorphoi Insofar as graft polymers are concerned the new azo line are illustrative of the benzomorpholine coupling compounds of our invention are of particular utility for compounds used in the preparation of the azo compounds dyeing fibers prepared from a graft polymer obtained by of our invention. I graft polymerizing ,acrylonitrile and an acrylamide or The azo compounds of our invention have varying methacrylamide with a preformed copolymer of acryloutility for the dyeing or coloration of cellulose alkyl nitrile andthe same or different acrylamide or methacrylcarboxylic acid esters having 2 to 4 carbon atoms in amide. the acid groups thereof nylon, wool, acrylom'trile graft U. S. Patent 2,620,324 issued December 2, 1952, U. S. polymers and polyesters such as polyethylene terephthal- Patent 2,649,434 issued August 18, 1953 and U. S. Patent ate. 2,657,191 issued October 27, 1953 disclose other typical The monoazo compounds of our invention are dyes for graft polymers that can be dyed with the new azo comfibers prepared from graft polymers obtained by graft pounds of our invention. polymerizing acrylonitrile alone or together with one or The 2 -'amino 4 alkylsulfonyl 5 nitrothiazole more other monoethylenic monomers with a preformed compounds used in the preparation of the azo compounds polymer. The preformed polymer can be a homopolyof our invention are new compounds. They are premer (a polymer prepared by polymerization ofa single pared in accordance with the following series of reactions.

As seen from the foregoing 2-acetamido-4,5-diiodothiazole [JACS, 71, 4007 (1949)] is nitrated with nitric acid to obtain 2acetamido-4-iodo-S-nitrothiazole which monomer) or it can be an interpolymer such as a copolymer (a polymer prepared by the simultaneous po1ymerization in a single reaction mixture of two monomers) or a terpolymer (a polymer prepared by the simultaneous is reacted with a sodium alkyl mercaptide to form a 2- polymerization in a single reaction mixture of three fl am 4 alkylm rcapto 5 nitr thiaz l 00mrnonomers), or the like, and the graft polymers for which 40 p This letter compound is treated with hydrogen the dyes are particularly useful are tho e containing t peroxide to obtain a 2-acetamido-4alkylsulfonyl-S-nitroleast 5% by Weight of combi d acrylonitrile grafted thiazole compound which is hydrolyzed with hydrochloric to the preformed polymer mole ule, acid to form the desired 2-amino-4-alkylsulfonyl-S-nitro- The graft polymers which can be dyed are thus polyihialoie compound- The Prepaiation 0f the new mers having directed placement f th l i d amino-4-alkylsulfonyl-5nitrothiazole compounds is illusmonomeric units in the raft polymer l l as di trated hereinafter with reference to the preparation of tinguished from the random distribution obtained in 2 amine 4 n biiiyisllifohyi 5 hiiioihiazoie, 2 interpolymers which are prepared by simultaneous polyamine 4 meihyisilifonyi 5 niifeihialoie a merization of all of the monomeric materials in the amine-4-eihYiSn1f0ny1-5-niirOthiaZOlepolymer. The preformed polymercan be either a homo- The following examples illustrate the new compounds polymer of any of the well-kn l i bl of our invention and the manner in which they are preomers containing a single CH=C group and desirably P a CH =C group, or an interpolymer of two or more EXAMPLE 1 of such monomers; and the grafting can be effected with the preformed homopolymer or interpolymer in the poly- 55 grams of 2-aeeian1id0-4fi-diiOdOihiaZOie were merization mixture in which it was formed (i. e. a live nitraied to replace group with hiil'o group y polymer) or with the preformed polymer isolated from adding it siowiy i0 of filming nim'e acid the polymerization mixture in which it was formed (Le. a Afief Standing at this temPei'atiife a d d polymer) for 2 hours, the reaction mixture was allowed to come h r f r d polymer desirably is a homopolymer 60 to room temperature and was then poured onto ice. The of a vinyl pyridine, an acrylamide, a maleamide, a fumardark Slurry resulting was mzide weakly baslc wlth NH4OH amide, an acrylate, a methacrylamide, a methacrylate, an filtered and yellow sohd recqvered on the-filter itaconamide, a citraconamide, a fumaramate, an itaconawashed Y wlt-h Water and dned' The yellow Sohd mate, a citraconamate, a maleamate, or a vinyl ester; or timS-obtamed Welghed grams (85%) Band on crystal an interpolymer of two or more of such monomers with hzauon from ethyl alcohol gave yellow needles of 2- acetamido-4-iodo-S-nitrothiazole melting at 245 C.- each other or of at least one of such monomers with one 247 C. or more dlfierent monoethylemc monomers characterized C l l d; C 193; H, 13; N, 1, 40,7 S 1( 3 by a CH=C group such as styrene, acrylonitrile, i

Found: C, 19.21; H, 1.48; N, 12.92; I, 39.05; S, 9.94. substituted styrenes, vinyl or vlnylldene chlorldes, vinyl 7 6.3 grams of the above 2-acetamido-4-iodo-5-nitrothiazole in 25 cc. of ethyl alcohol were refluxed 10 hours rates, acrylic acid, methacrylic acid, substituted acrylowith 2.64 grams of sodium n-butylmercaptide in 75 cc. nltrile, furnaronitrile, ethylene and the like. i of ethyl alcohol under nitrogen. Partial concentration The graft polymerization is effected by polymerizing and filtration yielded 5.7 grams of crude 2-acetamido-4- acrylonitrile or a mixture of acrylonitrile with any other l5, n-butylmercapto-S-nitrothiazole which, when crystallized from ethyl alcohol and then from acetic acid, yielded 3.4 grams (62%) of pure 2-acetamido-4-n-butylmercapto-5- nitrothiazole in the form of yellow crystals melting at 213 C.-215 C.

Calculated: C, 39.28; H, 4.72; 15.27; S, 23.27. Found: C, 39.45; H, 4.78; N, 14.88; S, 23.08.

5.5 grams of 2-acetamido-4-n-hutyhnercapto-S-nitrothiazole obtained as described above were reacted with 16 grams of 30% H 02 in 40 cc. of acetic acid, first at room temperature for 1 hour, and then at 80C. for 2 hours. On cooling and filtering 5.7 grams (92%) of 2- acetamido-4-n-butylsulfonyl-S- nitrothiazole were obtained in the form of yellow needles. Upon recrystallization from aqueous ethyl alcohol the 2-acetamido-4-nbutylsulfonyl-S-nitrothiazole was obtained in the form of bright, pale yellow plates melting at 165 C.167 C.

Calculated: C, 35.18; H, 4.27; N. 13.67; S, 20.85. Found: C, 35.23; H, 4.23; N, 13.15; S, 20.80.

The 2-acetamido-4-n-butylsulfonyl-S-nitrothiazole obtained as described above was hydrolyzed by refluxing with dilute aqueous methanolic HCl for 2 hours. Partial concentration of the reaction mixture yielded 2-amino-4- n-butylsulfonyl-S-nitrothiazole, a yellow solid.

EXAMPLE 2 By the use of an equivalent amount of sodium methylmercaptide, sodium ethylmercaptide and sodium n-propylmercaptide, respectively, for sodium n-butyl mercaptide in Example 1 2-amino-4-methylsulfonyl-S-nitrothiazole, 2- amino-4-ethylsulfonyl-S-nitrothiazole and 2 arnino-4-npropylsulfonyl-S-nitrothiazole, respectively, are obtained.

EXAMPLE 3 6.3 grams of 2-acetamido-4-iodo-5-nitrothiazole, obtained as described in Example 1, in 25 cc. of ethyl alcohol were refluxed hours with 1.5 grams of sodium methylmercaptide in 75 cc. of ethyl alcohol under. nitrogen. Partial concentration and filtration yielded yellow crystals of 2-acetamido-4-methylmercapto-S-nitrothiazole. Crystallization from ethyl alcohol yielded 2.6 grams (70%) of 2-acetamido-4-methylmercapto-S-nitrothiazole melting at 237 C.-239 C.

The 2.6 grams of 2-acetamidoA-methylmercapto-S- nitrothiazole thus obtained were reacted with 16 grams of 30% H 0 in 40 cc. of acetic acid, first at room temperature for one hour, and then at 80 C. for 2-3 hours. Cooling and filtering yielded 2.7 grams of 2-acetamido-4- methylsulfonyl-S-nitrothiazole as yellow crystals.

The 2-acetamido-4-methylsulfonyl-S-nitrothiazole obtained as described above was hydrolyzed by refluxing with dilute aqueous methanolic HCl for 2-3 hours. Partial concentration and filtration yielded yellow crystalline 2-amino-4-methylsulfonyl-S-nitrothiazole.

EXAMPLE 4 6.3 grams of 2-acetamido-4-iodo-5-nitrothiazole, obtained as described in Example 1, in cc. of ethyl alcohol were refluxed 10 hours with 1.7 grams of sodium ethylmercaptide in 75 cc. of ethyl alcohol under a nitrogen atmosphere. Concentration to one-quarter of the original volume, followed by cooling and filtration, yielded 3.7 grams of yellow crystals of 2-acetamido-4-ethylmercapto- S-nitrothiazole. Crystallization from ethyl alcohol yielded yellow crystals of 2-acetamido-4- ethylmercapto-S-nitrothiazole melting at 221 C.223 C.

The 2-acetamido-4-ethylmercapto-S-nitrothiazole thus obtained was reacted with 16 grams of H 0 in cc. of acetic acid, first at room temperature for 1 hour, and then at 80 C. for 2 hours. On cooling and filtering Z-acetamido-4-ethylsulfonyl-5-nitrothiazole was obtained in the form of yellow crystals.

EXAMPLE. 5

A. Preparation of nitrosyl sulfuric acid 1.52 grams of sodium nitrite were added portionwise,

with vigorous stirring, to 10 co of concentrated sulfuric acid (-96%) and the temperature of the reaction mixture Was allowed to rise no higher than 65 C. The resulting solution was then cooled to 5 C. and 20 cc. of a mixture of 3 cc. of n-propionic acid and 17 cc. of acetic acid were added dropwise, with stirring, while allowing the temperature to rise to 15 C. and maintaining it at this temperature during the remainder of the addition.

B. Diazotization The nitrosyl sulfuric acid mixture prepared as described above was cooled to 0 C.5 C. and then 5.3 grams (0.02 mole) of 2-amino-4-n-butylsulfonyl-S-nitrothiazole were added portionwise while stirring, after which 20 cc. more of the n-propionic-acetic acid mixture described above were added while keeping the temperature of the reaction mixture at 0 C.- 5 C. The reaction mixture thus obtained was then stirred at 0 C.5 C. for 2 hours and the excess sodium nitrite present in the mixture was destroyed by adding 0.5 gram of urea. A clear diazonium solution was obtained.

C. Coupling 10 cc. (.004 mole) of the 2-amino-4-n-butylsulfonyl-S- nitrothiazole diazonium solution prepared as described in B above were added, with stirring, at 0 C.-5 -C. to a solution of 0.94 gram (.004 mole) of 1-fi,' -dihydroxypropyl 2,7-dimethyltetrahydroquincline in 7 cc. of 10% sulfuric acid cooled to 0 C. The couplingreaction which takes place was allowed to proceed for .15 to 30 minutes and then the reaction mixture was drowned in 200 cc. of Water with stirring. After the reaction mixture thus obtained had stood for about 1 hour, the precipitated dye compound was recovered by filtration, washed well with water and dried. The dye compound thus obtained has the formula:

CHIgCHQHCHzOH It dyes cellulose acetate, wool, nylon and polyethylene terephthalate textile materials and textile materials made of the acrylonitrile graft polymer specifically described hereinafter blue-green shades.

EXAMPLE 6 4.46 grams 0.02 mole) of 2-amino-4-methylsulfonyl-5- nitrothiazole were diazotized exactly in accordance with the procedure described in Example 5 in connection with the diazotization of 2-amino-4-n-butylsulfonyl-5-nitro- 'thiazole.

10 cc. (0.89 gram i. c. 0.004 mole) of the 2-amino4- methylsulfonyl-S-nitrothiazole diazonium solution prepared as described above were added, with stirring, at 0 C.-5 C. to a solution of 0.94 grams of l,8,'y-dihydroxypropy1-2,7-dimethyltetrahydroquinoline in 7 cc. of 10% sulfuric acid cooled to 0 C. The coupling reaction which takes place was allowed to proceed for 15 to 30 minutes and then the reaction mixture was drowned in 200 cc. of water with stirring. After the reaction mixture thus obtained had stood for about 1 hour the precipitated dye compound was recovered by filtration, washed well with water and dried. The dye compound thus obtained dyes cellulose acetate, nylon, wool, Dacron textile materials and textile materials made of the acrylonitrile graft polymer specifically described hereinafter deep blue-green shades.

EXAMPLE 7 were. coupled with 0.71 grams of 'l-,8 hydroxyethy1tetrahydroquinoline in solution in 7 cc. of 10% sulfuric acid. Coupling and recovery of the dye compound formed were carried out in accordance with the procedure described in Example 5. The dye compound obtained colors cellulose acetate, nylon, wool, Dacron textile materials and textile materials made of the acrylonitrile graft polymer specifically described hereinafter blue shades.

EXAMPLE 8 A solution of 0.64 grams of S-phenyI-S-pyrazolone in acetic acid was coupled with 10 cc. of the 2-amino-4-"nbutylsulfonyl-j-nitrothiazole diazonium solution prepared as described in Example 5. Coupling and recovery of the dye compound formed were carried out in accordance withthe procedure described in Example 5. The dye compound obtained colors cellulose acetate, nylon, wool, Dacron textile materials and textile materials made of the acrylonitrile graft polymer specifically described hereinafter orange-red shades and has good affinity for the aforesaid materials. 7

EXAMPLE 9,

10 cc. of a 2-amino-4-n-butylsulfonyl-5-nitrothiazole diazonium solution prepared as described in Example 5 were added, with stirring, at C. C. to a solution of 0.58 grams of thiobarbituric acid in 7 cc. of an aceticpropionic acid mixture '(prepared as described in Example 5) cooled to 0 C. The coupling reaction which takes place was allowed to proceed for 1 hour after which the reaction mixture was made neutral to Congo red paper by the addition of sodium carbonate and drowned in 200 cc. of water with stirring. The dye compound which precipitated was recovered by filtration, washed well with water and dried. 1.1 gram of a dye compound having the formula:

was thus obtained. orange shades.

It colors cellulose acetate yellow- EXAMPLE By the use of 0.51 grams of 2iminobarbituric acid in place of thiobarbituric acid in Example 9 a good yield of a dye compound which colors cellulose acetate yelloworange shades is obtained.

EXAMPLE 12 By the use of 0.57 grams of 4-iminothiobarbituric acid in place of thiobarbituric acid in Example 9 a good yield of a dye compound which colors cellulose acetate yelloworange shades is obtained.

EXAMPLE 13 10 cc. of a 2-amino-4-n-butylsulfonyl-S-nitrothiazole diazonium solution prepared as described in Example 5 were added, with stirring, at 0 C.5 C. to a solution of 0.95 grams (.004 mole) of 1-/8,'y-dihydroxypropyl-2,5- dimethylbenzomorpholine in 7 cc. of 10% sulfuric acid cooled to 0 C. The coupling reaction which takes place was allowed to proceed for to minutes and then the reaction mixture was drowned in 200 cc. of water with stirring. After the reaction mixture thus obtained had stood for about 1 hour, the precipitated dye compound was recovered by filtration, washed well with water and dried. The dye compound thus obtained colors cellulose acetate, wool, nylon and polyethylene terephthalate textile materials and textile materials made of the acrylonitrile graft polymer specifically described hereinafter blue-green shades.

The following tabulation further illustrates the compounds included within the scope of our invention together with the color they produce on cellulose acetate silk. The compounds indicated below may he prepared by diazotizing the amines listed under the heading Amine and coupling the diazonium compounds obtained with the compounds specified in the column entitled Coupling Component. The diazotization and coupling reactions may, for example, be carried out following the general procedure indicated hereinbefore.

Amine Coupling Component Color 2 amino 4 methylsul- 1. tetrahydroquinollne violet blue.

fonyl-5-nitrothlazolo.

Do 2. l-methyltetrahydroquingreenisholine. blue. Do 3. 1- 8 hydroxyethyltetra- D0.

hydroquinoline. Do 4. 1-fl,-/-dihyd1oxypropyl- Do.

tetrahydroquinoline. Do 5. 1 5 hydroxybutyltctra- D0.

hydroquinoline. Do 0. 1- 13, 'y dihydroxypropyl- Do.

2 methyltetrahydroquinoline.

Do 7. 1 -fi, 'y dihydroxypropy1- blue-green.

7 methyltetrahydroqumoline. D0 8. 1 B, 'y dihydroxypropyl blue.

' iih-lchlorotetrahydroqulnoe. .Do 9. 1 B methyl B, y dlhygreenishdroxypropyltetrahydroblue. quinoline. Do 10. l-fl-methoxyethyltetra- D0.

hydroquinoline. Do 11. 1-B-cyanoethyltetrahy violet-blue. droquinoline. Do 12. 1 -59 carboethoxyethylblue. tetrahydroquinoline.

Do 13. 1 2, 2, 2 trifiuoroethylviolet blue.

hydroquinoline. Do 14. l-2,2-difiuoroethyltetra- Do.

hydroquinoline. 15. 1 allyltetrahydroqulnogreenishltne. blue. 16. benzomorpholine v1olet -blue 17. 1 ethylbenzoruorphogreenishne. blue. 18. 1 B hydroxyethylben- Do.

zomorpholine. 19. 1-fl,'y-dlhydroxypr0pyl- D0.

benzomorpholine. 20. l-y-hydroxypropylben- Do.

zomorpholine. 21. 1-B-methylfl, -dlhy- Do.

droxypropylbenzomorphoe. 22. l-fl',y-dihydroxypropylbluish green.

2-methy1benzo1norphoe. 23. l-fi -dihydroxypropylq- Do.

methylbenzomorpholine. Do 24. 148yy-dihydroxypropyl-7- blue.

chlorobenzomorpholine. Do 25. 1- 3,'y-dihydroxypropyl-7- D0.

ethoxybenzomorpholine. Do 26. l-fl-ethoxyethylbenzoblulsh green.

mcrpholine. Do 27. 1 B cyanoethylbenzoviolet-blue.

morpholine. Do 28. l-B-carboethoxyethylbenblue.

zomorpholine. Do 29. 1-2,2,2-trifiuoroethylbenviolet-blue. zomorpholine. Do 30. 1-2,2-difiuoroethylbenzo- D0.

morpholine. 31. l-allylbenzomorpholina. grofimshue. 32. barbiturie aeid orange. 33. thiobarbituric aci yelloworange. 34. Z-imlnobarbiturie acid Do. 35. 4-iminothiobarbitnrlc D0.

acid. 36. 3-methyl-5-pyrazolone orange-red. 37. 3-trifiuoromethy1-5-py- Do.

razolone. 38. 3 carboethoxy-5-pyrazo- D0.

lone. 39. l-phenyl-3-methyl-5-py- D0.

razolone. 40. l-phenyl-S-amiuo-S-py- Do.

razolone. 2-amiuo-4-ubutylsulf0nyl- 41. tetrahydroquinoliue. violet-blue.

5-nitrothlazole.

Don... 42. 1 -'methyltetrahydro greenishquinoline. blue. Do 43. 1-fl, -dihydroxypropyl- Do. tetrahydroqu'moline. Y

Amine Coupling Component Color 2-amino-4-n-buty1sulfo- 44. 1 6 hydroxybutyltetragreenishnyl-5nitrothiazole. hydroquinoline. blue.

Do 45. 1-5, '7 dihydroxypropyl- Do.

% -methy1tetrahydroqulno- 46. 1-B,- -dihydrxypropylblue-green.

iii-lrlnethyltetrahydroqumo- 17. 1-8, y-dihydroxypropylblue.

ii;cholorotetrahydroquino- 48. 1 -fl-methyl-fi, 7 -dihygreenishdroxypropyltetra -hyc1ro blue. quinoline.

49. l-B-methoxyethyltetra- Do.

hydroquinoline.

50. 1-fl-eyanoethyltetrahyviolet-blue.

droquinoline.

61. 1 13 earboethoxyethylblue.

tetrahydroquinoline.

52. 1 2, 2, 2 trifiuoroethyl violet-blue.

tetrahydroquinoline.

53. 1 2, 2 difluoroethyltet- D0.

rahydroquinoline.

54. 1 allyltetrahydroquinogreenishline. blue.

55. benzomorpholine violet-blue.

56. l-ethylbenzomorpholine. grcenlsh- '57. 1 B hydroxyethylben- Do. zomorphollne.

58. l-Byy-dihydmxypropyl- D0.

benzomorphollne.

59. l-y-hydroxypropylben- Do.

zomorpholine.

ilfiloxypropylbenzomorphoe. 61. l-Byy-dihydroxypropyl- 2-n1ethylbenzomorpholine. 62. l-flwy-dihydroxypropyl- Do.

7-methylbenzomorpholine. 63. l-fl,'y-dihydroxypropylblue.

7-chlorobenzomorpholine. 64. 1-;8,-y-dihydroxypropyl- Do.

7-ethoxybenzomorpholine. 65. 1 -6 -ethoxyethylbenzobluish-green.

morpholine. 66. 1 B cyanoethylbenzoviolet-blue.

Inorp e. 67. 1 B carboethoxyethyl blue.

benzomorpholine. 68. 1 2, 2, 2 trifiuoroethylviolet-blue.

benzomorpholine. 69. 1 2, 2 difinoroethylben- Do.

zomorpholine. 70. 1-allylbenzomorpholine. grgtinlshno. 71. 3-methyl-5-pyrazolone.. orange-red. 72. S-trifluoromethyl-S-py- Do.

razolone. 73. 3-carboethoxy-5-Dyraz- Do.

olone. 74. 1- phenyl 3 methyl Do.

pyrazolone. 75. 1-phenyl-3-amino-5- orange.

pyrazolone. 76. 1-B,- -dihydroxypropy1- blue-green.

2,5-dimethylbenzomorpholine. 77. 3-carboxy-5-pyrazolone orange-red. 78. B-carbomethoxy-fi-py- Do.

razolone. 2 amino 4 methylsulfo- 79. 3-carboxy-5-pyrazolone. Do.

nyl-fi-nitrothiazole.

Do 80. 3-carbomethoxy-5-pyraz- Do.

olone.

When 2-amino-4-ethylsulfonyl-S-nitrothiazole, Z-amino- 4 n propylsulfonyl 5 nitrothiazole and 2-amino-4-isopropylsulfonyl-5-nitrothiazole, respectively, are diazotized and the diazonium compounds are coupled with each of the coupling components (1-40, 79 and 80) set forth in the above tabulation, monoazo compounds of our invention are obtained which color cellulose acetate generally similar shades as the corresponding monoazo dye obtained from diazotized 2-a1nino-4-methylsulfonyl-5-nitrothiazole. To illustrate, the monoazo compound prepared from diazotized 2-amino 4-ethylsulfonyl-S-nitrothiazole and 1-B,' -dihydroxypropyl-2,S-dimethylbenzomorpholine colors cellulose acetate bluish-green shades as does the corresponding monoazo compound prepared from diazotized 2-amino-4-methylsulfonyl-S-nitrothiazole and l-Bgydihydroxypropyl-Z,S-dimethylbenzomorpholine.

Other pyrazolone compounds, in addition to those indicated hereinbefore, that can be used in the preparation of the azo compounds of our invention include, for example,

bluish-green.

3amino-5-pyrazolone, 3-hydroxy-5-pyrazolone, l-phenyl- 3 hydroxy 5 pyrazolone, 1 phenyl 3 methyl 5- p-nitrophenyl pyrazolone, 3-phenyl-5-pyrazolone, 1- phenyl 3 carbomethoxy 5 pyrazolone, 1 pheny1-3- carboethoxy 5 pyrazolone, 1 phenyl 3 carboethoxy- 5 pyrazolone, 1,3 dimethyl 5 pyrazolone, 1 p nitrophenyl 3 methyl 5 pyrazolone, 1 o nitrophenyl 3 methyl 5 pyrazolone, 1 p methylphenyl- 3 methyl 5 pyrazolone, 1 p methoxyphenyl 3- amino 5 pyrazolone, 1 p methylphenyl 3 amino- 5 pyrazolcne, l o chlorophenyl 3 amino 5 pyrazolonc, l p chlorophenyl 3 amino 5 pyrazolone, 1 p ethylphenyl 3 methyl 5 pyrazolone and 1 pchlorophenyl-3-methyl-pyrazolone.

Preparation of acrylonitrile graft polymer 3.0 g. of acrylonitrile' and 7.0 g. of N-methyl methacrylamide were emulsified in 40 cc. of water containing 0.15 g. of potassium persulfate and 0.01 g. of tertiary dodecyl mercaptan. The emulsion was heated at 60 C. until 94% or more of the monomers had copolymerized. This result is usually accomplished by heating for about 12 hours. The copolymer contained approximately by weight of acrylonitrile and 70% by weight of N-methyl methacrylamide. The mixture was then cooled to room temperature, 50 cc. of water added and the mixture agitated until a homogeneous solution of dope containing 10% by weight of the copolymer resulted.

30.7 g. (3.07 g. of copolymer) of the above prepared solution or dope of the copolymer were placed in a jacketed reactor provided with an agitator and heat exchanger. There were then added 10 g. of acrylonitrile, 114 cc. of water, 0.58 g. of 85% phosphoric acid, 0.1 g. of potassium persulfate, 0.17 g. of potassium metabisulfite, 0.1 g. of tertiary dodecyl mercaptan and 0.56 g. of a 30% solution in water of N-methyl methacrylamide and the mixture heated, with stirring, to C. and then allowed to level oil at 37-39 C. After the heat of polymerization had been removed and when the conversion of the acrylonitrile to polymer had reached 96% or more, which is usually accomplished in a period of about 12 hours, the temperature was raised to 90 C. The mother liquor was removed by centrifuging the polymerization mixture, the polymer precipitate being reslurried twice with water and centrifuged to a 70% 'moisture cake. The cake was dried under vacuum at 80 C. in an agitated dryer. The over-all yield of modified polyacrylonitrile product was over 90%. After hammer-milling, the dry powder, now ready for spinning, was stored in a moisture proof container.

The acrylonitrile graft polymer prepared as above and containing about 18% by weight of N-methyl methacrylamide was soluble in N,N-dimethylformamide. Fibers spun by extruding a solution of the polymer product in N,N-dimethylformamide into a precipitating bath had a softening temperature of about 240 C., an extensibility of about 20-30 percent depending on the drafting and relaxing conditions, and showed excellent aifinity for dyes.

The monoazo dye compounds of our invention can be applied to cellulose alkyl carboxylic acid esters having 2 to 4 carbon atoms in the acid groups thereof, nylon, wool, acrylonitrile graft polymers, and polyester, such as polyethylene terephthalate, textile materials in the form of an aqueous dispersion and are ordinarily so applied. To illustrate, the dye compound is finely ground with a dispersing agent such as sodium lignin sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dyebath thus prepared is heated to a temperature approximating C. C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to C.- C. and maintained at this temperature until dyeing is complete, usually one-half to two hours. From time to time throughout the dyeing operation, the material is worked to promote even dyeing.

1 1 Upon completion of the dyeing operation, the textile material is removed from the dyebath, Washed with an aqueous soap solution, rinsed well with water and dried.

In the case of certain of the acrylonitrile graft polymers described hereinbefore it is necessary to dye at the boil for an extended period of time. Instances may be encountered where the fiber is not satisfactorily colored by the dyeing procedure just described. In these instances special dyeing techniques, such as the use of pressure, for example, developed by the art for the coloration of materials ditficult to color may be employed.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, /3 to 3% (by Weight) of that of the textile material although lesser or greater amounts of the dye can be employed.

The following example illustrates one satisfactory way in which the fibers of the acrylonitrile graft polymers can be dyed using the azo compounds of our invention. 16 milligrams of dye are ground with an aqueous solution of sodium lignin sulfonate until well dispersed or alternately the dye can be dissolved in cc. of hot Cellosolve (i. e. ethylene glycol monoethyl ether). The dispersion or solution, as the case may be, is then poured into 150 cc. of water to which a small amount of surface-active agent such as Igepon T (C H -CO-N(CH )-C H SO Na) Nekal BX (sodium alkylnaphthalene-sulfonate) or Orvus (sodium lauryl sulfate-type) has been added. The dyebath is then brought to the desired temperature and 5 "12 grams of well wet-out fibers of the graft polymer are added thereto. Dyeing is continued until the proper shade is reached. From time to time throughout the dyeing operation, the material is worked to promote even References Cited in the file of this patent UNITED STATES PATENTS 2,149,051 Helberger et a1 Feb. 28, 1939 2,345,010 Seymour et al Mar. 28, 1944 2,386,599 Dickey et a1. Oct. 9, 1945 2,578,290 Dickey et a1 Dec. 11, 1951 2,659,719

Dickey et al Nov. 17, 1953 

